CN110707220B - Method for improving stability of perovskite battery through black phosphorus - Google Patents

Method for improving stability of perovskite battery through black phosphorus Download PDF

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CN110707220B
CN110707220B CN201810747373.3A CN201810747373A CN110707220B CN 110707220 B CN110707220 B CN 110707220B CN 201810747373 A CN201810747373 A CN 201810747373A CN 110707220 B CN110707220 B CN 110707220B
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black phosphorus
perovskite
precursor solution
stability
improving
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CN110707220A (en
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赵一新
王勇
钱旭芳
张太阳
阚淼
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Shanghai Jiaotong University
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    • H10K71/30Doping active layers, e.g. electron transporting layers

Abstract

The invention provides a method for improving the stability of a perovskite battery through black phosphorus; the method comprises the following steps: dispersing two-dimensional material black phosphorus in DMF to obtain black phosphorus dispersion liquid; mixing MAI and PbI2After mixingDissolving the mixture in DMSO, adding DMF and the black phosphorus dispersion solution, and uniformly mixing to obtain a precursor solution; and spin-coating the precursor solution on the surface of the perovskite substrate, and then carrying out low-temperature annealing to obtain the perovskite thin film. The invention has the following beneficial effects: the black phosphorus used in the invention is commercialized, cheap and easy to obtain; the method is convenient and fast to operate, and the high-quality perovskite thin film can be obtained by a one-step method by adding a small amount of black phosphorus into the traditional perovskite precursor solution, so that the requirement of large-scale industrial production can be met; the efficiency of the battery assembled by the perovskite thin film containing the two-dimensional material black phosphorus obtained by the invention is as high as 20.65%, and the efficiency is not reduced at all after a 500-hour continuous illumination experiment.

Description

Method for improving stability of perovskite battery through black phosphorus
Technical Field
The invention belongs to the technical field of energy and materials, and particularly relates to a method for improving the stability of a perovskite battery through black phosphorus.
Background
The solar cell using the photovoltaic effect as the working principle can directly convert solar energy into electric energy, and is one of the most potential technologies for solving the energy crisis. 2012, all-solid-state organic-inorganic hybrid lead-halogen perovskite CH3NH3PbI3(MAPbI3) The solar cell (perovskite cell for short) is one of ten major technological breakthroughs of the Science magazine selection in 2013 by virtue of the different military prominence of the advantages of high efficiency, low cost and simple and convenient production process, and the efficiency of the perovskite photovoltaic device is rapidly improved in the last 5 years. In the latest certification chart of the efficiency of the solar cell published by NREL in 2017, the certification efficiency of the perovskite cell is as high as 22.7%.
At the beginning of development of perovskite, most laboratory high-efficiency perovskite cells have effective areas of less than 0.1cm2. With the rapid development of the field of perovskite, the effective area of perovskite is also increasing. In 2017, the Korean gifts team published 36cm of the article reported on Nature (Nature, 2017, 550(7674))2An efficiency of 12% has been achieved for an active area perovskite cell. The Huangjinsong team works in the near termIt is found in Nature energy, doi:10.1038/s41560-018-0153-9 that a good perovskite thin film cannot be obtained and defects can be passivated to a certain extent by adding a certain amount of surfactant in the blade coating process of a large-area perovskite battery. By this method, they had an effective area of 57cm2The photoelectric conversion efficiency of 14.6% is achieved on the perovskite cell module. It is not hard to discover from these studies that most groups in recent years have no longer been limited to high efficiencies on small area perovskite cells, whose area has been increasing, while also achieving considerable photoelectric conversion efficiencies.
Perovskite cells have been close to commercialization from a large area, high efficiency perspective. While these problems have been addressed, another important issue that has hindered the commercialization of perovskite cells has begun to manifest itself in long-term stability. Currently, a number of studies indicate that the wet stability of perovskite batteries can be solved by improving the battery packaging technology or by surface passivation technology (atomic layer deposition). At this time, the problem of stability of perovskite batteries under practical operating conditions, i.e., under long-term lighting conditions, is undoubtedly the biggest obstacle to the commercialization progress of novel batteries such as perovskite.
Disclosure of Invention
The invention aims to provide a method for improving the stability of a perovskite battery through black phosphorus, and particularly relates to in-situ introduction of the black phosphorus into a perovskite layer. The black phosphorus is used as a nucleation core in the growth process of the perovskite crystal grains, induces the nucleation and growth of the perovskite crystal grains, and is finally distributed among the perovskite crystal grains, so that the perovskite solar cell obtains good results in the aspects of photoelectric conversion efficiency, particularly illumination stability.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a method for improving the stability of a perovskite battery through black phosphorus, which comprises the following steps:
dispersing black phosphorus in N, N-Dimethylformamide (DMF) to obtain black phosphorus dispersion liquid;
mixing methylamine iodide (MAI) and lead iodide (PbI)2) MixingDissolving the mixture in dimethyl sulfoxide (DMSO), adding N, N-Dimethylformamide (DMF) and the black phosphorus dispersion liquid, and uniformly mixing to obtain a precursor solution;
and spin-coating the precursor solution on the surface of the perovskite substrate, and then annealing at low temperature to obtain the perovskite thin film.
Preferably, the mass concentration of the black phosphorus in the black phosphorus dispersion liquid is 0.1-0.5 g/L.
Preferably, in the precursor solution, MAI and PbI2The molar ratio of DMF to DMSO is 1:1, and the volume ratio of DMF to DMSO is 4: 1.
Preferably, the mass concentration of the black phosphorus in the precursor solution is 0.01-0.2 g/L.
Preferably, the spin coating speed is 3000-6000 rpm.
Preferably, 300-500 uL chlorobenzene is dripped in the spin coating process.
Preferably, the low-temperature annealing is carried out at the temperature of 90-110 ℃ for 10-20 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the black phosphorus used in the method is a new member of two-dimensional materials, has been commercialized, low in cost and easy to obtain after the rapid development of several years;
2. the method is convenient and fast to operate, and the high-quality perovskite thin film can be obtained by a one-step method by adding a small amount of black phosphorus into the traditional perovskite precursor solution, so that the requirement of large-scale industrial production can be met;
3. the efficiency of the perovskite battery assembled by the perovskite thin film containing the black phosphorus obtained by the invention is improved to 20.65 percent. More importantly, after a 500-hour continuous illumination experiment, the photoelectric conversion efficiency of the LED lamp is not reduced by one wire.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows inventive example 1 and a comparative example1 XRD pattern of the resulting perovskite thin film, wherein MAPbI30.02BP represents a film containing black phosphorus in the perovskite layer, and the concentration of the black phosphorus in the perovskite precursor solution is 0.02 g.L-1
FIG. 2 is an SEM image of perovskite thin films obtained in example 1 and comparative example 1; wherein a is an SEM image of the perovskite thin film of example 1, and b is an SEM image of the perovskite thin film of comparative example 1;
fig. 3 is a graph of the photoelectric conversion efficiency of the perovskite solar cell obtained in example 1;
FIG. 4 is a UV-visible absorption spectrum of the perovskite thin film used to prepare the perovskite cell used in example 2 and comparative example 1; wherein MAPbI30.05BP represents a film containing black phosphorus in the perovskite layer, and the concentration of the black phosphorus in the perovskite precursor solution is 0.05 g.L-1
FIG. 5 is a graph of the photoelectric conversion efficiency of the perovskite solar cells obtained in example 2 and comparative example 1; in the figure, curve 1 is MAPbI3/0.05 BP-based cell, curve 2 MAPbI3A base battery;
fig. 6 is a schematic diagram of changes in photoelectric conversion efficiency of the perovskite solar cells obtained in example 2 and comparative example 1 under continuous light conditions.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The preparation method of the perovskite substrate comprises the following steps: after FTO glass is etched by concentrated hydrochloric acid and zinc powder, TiO is sprayed in sequence2Dense layer and spin-coated SnO2And (5) a plane layer is obtained.
Example 1
The embodiment relates to a method for adding a two-dimensional material black phosphorus dispersion liquid into a precursor and further obtaining a perovskite thin film through spin coating, which comprises the following steps:
s1, dispersing the two-dimensional material black phosphorus in DMF, and performing ultrasonic treatment at 20-30 ℃ for 1-3 h to obtain 0.1g/L black phosphorus dispersion liquid;
s2, mixing MAI and PbI2Mixing according to the molar ratio of 1:1, dissolving in 400 μ L of DMSO, adding 1.2mL of DMF and 400 μ L of the black phosphorus dispersion prepared in the step S1, and uniformly mixing to obtain a precursor solution;
s3, spin-coating the black phosphorus-containing perovskite precursor solution on the surface of the perovskite substrate for 20S at the rotating speed of 5000rpm, wherein 400uL of chlorobenzene is dropwise added 17S before the end of the spin-coating time, and annealing is carried out for 20min at 100 ℃ after the spin-coating is finished, so that the perovskite thin film is obtained.
The surface of the perovskite thin film formed in step S3 is spin-coated with a hole transport layer, and a counter electrode silver or the like is vapor-deposited on the hole transport layer, and the manufacturing process of the solar cell can be referred to in the current literature.
Fig. 1 provides an X-ray map of example 1 from which it can be seen that the introduction of black phosphorus into the perovskite layer has no significant effect on the crystal form, crystallinity of the perovskite. FIG. 2a provides a scanning photograph of example 1, which shows that after adding black phosphorus, a two-dimensional material, to the perovskite precursor, the film appears dense and the grains become slightly larger. Fig. 3 provides a graphical representation of the photoelectric conversion efficiency of example 1, from which it is found that the perovskite cell with the addition of black phosphorus has a photoelectric conversion efficiency of 19.67%, which is considerable.
Example 2
The method of this example is the same as example 1 except that the concentration of black phosphorus is 0.02 mg/mL-1Increased to 0.05 mg. multidot.mL-1From FIG. 4, it can be found that the concentration of black phosphorus was increased to 0.05 mg/mL-1The addition of black phosphorus does not result in a change in the ultraviolet-visible absorption spectrum of the perovskite thin film. As can be seen from fig. 5, the efficiency of the black phosphorus-containing perovskite cell is as high as 20.65%. Table 1 shows the photovoltaic parameters of example 2, short circuit current (J) for solar cells made with black phosphorus-containing perovskite thin filmssc) Has obviously improved Fill Factor (FF) and photoelectric conversion efficiencyThe ratio was 20.65%. Fig. 6 shows a schematic diagram of the change of the photoelectric conversion efficiency of the perovskite battery containing black phosphorus under the condition of continuous illumination. From fig. 6, it can be seen that, after the illumination experiment for 500 continuous hours, the photoelectric conversion efficiency of the perovskite cell added with black phosphorus does not decrease.
Comparative example 1
The comparative process differs from example 1 in that the precursor solution does not contain black phosphorus. From table 1 it can be seen that the efficiency of the resulting perovskite cells is reduced. Fig. 2b provides a scanned photograph of comparative example 1, showing that the grains of the perovskite thin film to which no black phosphorus is added are significantly non-uniform. From FIG. 5, it can be found that with the addition of MAPbI3Under the same illumination condition, after 14 days of continuous illumination, the photoelectric conversion efficiency of the perovskite battery without the added black phosphorus is reduced by nearly 30% compared with the initial value.
TABLE 1
Figure GDA0003246294310000041
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (6)

1. A method for improving the stability of a perovskite battery through two-dimensional black phosphorus, the method comprising the steps of:
dispersing two-dimensional black phosphorus in N, N-dimethylformamide to obtain a two-dimensional black phosphorus dispersion liquid;
mixing methylamine iodide and lead iodide, dissolving the mixture in dimethyl sulfoxide, adding N, N-dimethylformamide and the two-dimensional black phosphorus dispersion liquid, and uniformly mixing to obtain a precursor solution;
spin-coating the precursor solution on the surface of a perovskite substrate, and then annealing at low temperature to obtain a perovskite thin film;
the mass concentration of the two-dimensional black phosphorus in the black phosphorus dispersion liquid is 0.1-0.5 g/L.
2. The method for improving the stability of a perovskite battery through two-dimensional black phosphorus according to claim 1, wherein the molar ratio of methylamine iodide to lead iodide in the precursor solution is 1:1, and the volume ratio of N, N-dimethylformamide to dimethyl sulfoxide is 4: 1.
3. The method for improving the stability of the perovskite battery through two-dimensional black phosphorus according to claim 1, wherein the mass concentration of the black phosphorus in the precursor solution is 0.02-0.2 g/L.
4. The method for improving the stability of the perovskite battery through two-dimensional black phosphorus according to claim 1, wherein the spin coating is performed at a rotating speed of 3000-6000 rpm.
5. The method for improving the stability of the perovskite battery through two-dimensional black phosphorus according to claim 1 or 4, wherein 300-500 uL chlorobenzene is dripped in the spin coating process.
6. The method for improving the stability of the perovskite battery through two-dimensional black phosphorus according to claim 1, wherein the low-temperature annealing is performed at 90-110 ℃ for 10-20 min.
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CN106129256A (en) * 2016-08-30 2016-11-16 戚明海 A kind of perovskite solaode with black phosphorus as hole transmission layer and preparation method
CN107104190A (en) * 2017-06-23 2017-08-29 中南大学 A kind of flexible perovskite solar cell and preparation method thereof
CN107887511A (en) * 2017-11-22 2018-04-06 苏州大学 A kind of method that perovskite solar cell is prepared based on two-dimensional material graphene phase carbon nitride

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CN106129256A (en) * 2016-08-30 2016-11-16 戚明海 A kind of perovskite solaode with black phosphorus as hole transmission layer and preparation method
CN107104190A (en) * 2017-06-23 2017-08-29 中南大学 A kind of flexible perovskite solar cell and preparation method thereof
CN107887511A (en) * 2017-11-22 2018-04-06 苏州大学 A kind of method that perovskite solar cell is prepared based on two-dimensional material graphene phase carbon nitride

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